Composition for preparing electroconductive resins

ABSTRACT

1. A COMPOSITION FOR PREPARING ELECTROCONDUCTIVE RESIN WHICH COMPRISES: (A) ONE OR MORE MEMBERS SELECTED FROM THE GROUP CONSISTING OF: (I) COMPOUNDS REPRESENTED BY THE FOLLOWING GENERAL FORMULA:   (H2C=C(-R1)-COO-(C(-R2)(-R3))N-SO3)X-M1   IN WHICH R1 IS A HYDROGEN ATOM OR A METHYL GROUP; EACH OF R2 AND R3 IS A HYDROGEN OR HALOGEN ATOM; N IS AN INTEGER FROM 1 TO 5; X IS AN INTEGER FROM 1 TO 3; AND M1 IS A HYDROGEN ATOM, NA, LI, K, AG, CU, MG, CA, ZN, BA, AL, AMMONIUM OR AMINE, (II) COMPOUNDS REPRESENTED BY THE FOLLOWING GENERAL FORMULA:   H2C=C(-R4)-COO-(C(-R5)(-R6))P-O-P(=O)(-O-M2)-O-M3   IN WHICH R4 IS A HYDROGEN ATOM OR A METHYL GROUP; EACH OF R5 AND R6 IS A HYDROGEN OR HALOGEN ATOM; P IS AN INTEGER FROM 1 TO 4; AND EACH OF M2 AND M3 IS A HYDROGEN ATOM, NA, LI, K, AG, AMMONIUM OR AMINE, AND (III) COMPOUNDS REPRESENTED BY THE FOLLOWING GENERAL FORMULA:   ((H2C=C(-R7)-COO-(C(-R9)(-R8))Q-O)2-P(=O)-O)X-M3   IN WHICH R7 IS A HYDROGEN ATOM OR METHYL GROUP; EACH OF R8 AND R9 IS HYDROGEN OR HALOGEN ATOM; Q IS AN INTEGER FROM 1 TO 4; X IS AN INTEGER FROM 1 TO 3; AND M4 IS A HYDROGEN ATOM, NA, LI, K, AG, CU, MG, CA, ZN, BA, AL, AMMONIUM OR AMINE, AND (B) COMPOUNDS WHICH CONTAIN VICINAL EPOXY GROUPS IN THE MOLECULES.

United States Patent Office.

Patented Nov. 12, 1974 Int. Cl. ctist 3/50 U.S. Cl. 260--13 13 ClaimsABSTRACT OF THE DISCLOSURE A composition for preparing electroconductiveresins with excellent properties, which comprises:

(A) one or more members being selected from the group consisting of (I)alkylene sulfonic esters or alkylene sulfonate esters of acrylic acid ormethacrylic acid; (II) alkylene phosphoric esters or alkylene phosphateesters of acrylic acid or methacrylic acid; and (III) alkylenephosphoric diesters or alkylene phosphate diesters of acrylic acid ormethacrylic acid; and (B) the compounds which contain epoxy groups inthe molecules; and if necessary, (C) solvents, polymerization initiatorsand/ or photosensitizers.

This invention relates to composition for preparing electroconductiveresins.

Further the invention relates to the composition for preparing theelectroconductive resins which have excellent properties such aselectroconductivity, mechanical properties, solvent resistance, filmforming property, adhesiveness, transparency and wear resistance.

In the ordinary art, the resins which are added with dispersion ofelectroconductive materials, for example, metallic compounds orpolycyclic aromatic compounds; or the aqueous solutions of the resinscontaining polyvinyl benzyl quaternary ammonium salt, oligostyrenesulfonic acid or polyvinyl pyridine quaternary compound as theirprincipal components, are well known as composition for preparing theelectroconductive resins. However, the electroconductive films obtainedfrom the former resins are inferior in the transparency and mechanicalproperties, while in the latter solutions of the resins, the syntheticreactions to obtain such resins are difiicult to be carried out, and theelectroconductivities of the films obtained from such resins are low,and in addition to that the electroconductivities thereof decrease withthe lowering of the relative humidity. Further, the films are formed bythe evaporation of solvents as used, therefore the solvent resistance,mechanical properties, adhesiveness and wear resistance of such filmsare inferior.

Accordingly, the object of the present invention is to overcome theabove-mentioned defects in the ordinary compositions for preparing theelectroconductive film.

Pursuant to the above object, the present invention provides a novelcomposition for preparing the electroconductive resin which comprises:

(A) One or more members selected from the group consisting of:

(I) a compound represented by the following general formula, hereinafterreferred to as sulfonic ester:

R2 0 GH,=C t 0 tlt 0lN.

1's \I's Lil L in which R is a hydrogen atom or a methyl group; each ofR and R is a hydrogen or halogen atom; n is an integer from 1 to 5; x isan integer from 1 to 3; and M is a hydrogen atom, Na, Li, K, Ag, Cu, Mg,Ca, Zn, Ba, Al ammonium or amine, (II) a compound represented by thefollowing general formula, hereinafter referred to as phosphoric ester:

0 OM2 azaaohlaho in which R is a hydrogen atom or a methyl group each ofR and R is a hydrogen or halogen atom; 7 is an integer from 1 to 4; andeach of M and M is a hydrogen atom, Na, Li, K, Ag, ammonium or amine,and

(III) a compound represented by the following general formula,hereinafter referred to as phosphoric diester:

in which R is a hydrogen atom or a methyl group; each of R and R is ahydrogen or halogen atom; q is an integer from 1 to 4; x is an integerfrom 1 to 3; and M is a hydrogen atom, Na, Li, K, Ag, Cu, Mg, Ca, Zn,

Ba, Al, ammonium or amine and (B) A compound containing an epoxy groupin the molecule, hereinafter referred to as epoxy compound, as theprincipal components, and if necessary,

(C) A solvent, polymerization initiator and/or photosensitizer.

The above-mentioned sulfonic esters as used in the present invention arealkylene sulfonic esters or alkylene sulfonate esters of acrylic acid ormethacrylic acid. As for the alkylene sulfonic esters of acrylic acid ormethacrylic acid, for example, sulfomethylene acrylate, sulfoethyleneacrylate, sulfoethylene methacrylate, sulfotrimethylene acrylate,sulfoisopropylene acrylate, sulfotrimethylene methacrylate,sulfotetramethylene acrylate, sulfotetramethylene methacrylate andsulfopentamethylene acrylate may be used. And in case the integer n inthe foregoing general formula becomes more than 5, the reactivity of theethylenically unsaturated group of the sulfonic ester is decreased, andthe cross-linking property of the composition is almost lost. Theaforesaid alkylene sulfonate esters can be obtained by neutralizing thecorresponding alkylene sulfonic esters with bases or metal chlorides.The bases or the chlorides which can be used for the neutralization maybe, for example, sodium hydroxide, lithium hydroxide, potassiumhydroxide and silver perchloride as monovalent metallic bases or thechloride; copper hydroxide, magnesium chloride, calcium chloride, bariumchloride and zinc chloride as divalent metallic bases or the chlorides;and aluminum hydroxide as a trivalent metallic base. Further, there aremany other bases which can be used for the neutralization such asammonia, aliphatic amines and cyclic amines, for example,monomethylamine, dimethylamine, trimethylamine, monoethylamine,diethylamine, triethylamine, nbutylamine, monoethanolamine,diethanolamineand triethanolamine as aliphatic monoamines;ethyleuediamine as an aliphatic diamine; pyridine, morpholine andpiperidine as cyclic monoamines; and p-phenylenediamine as a cyclicdiamine. The neutralization can be carried out in accordance with thewell known method.

The phosphoric esters which are used in the present invention arealkylene phosphoric esters or alkylene phosphate esters of acrylic acidor methacrylic acid. As for the alkylene phosphoric esters of acrylicacid or methacrylic acid, for example, phosphoric ethyleneacrylate,phosphoric ethylenemethacrylate, phosphoric trimethyleneacrylate,phosphoric isopropylenemethacrylate, phosphorictrimethylenemethacrylate, phosphoric tetramethylenemethacrylate andphosphoric l-chloromethyl-ethylenemethacrylate may be used. In theforegoing general formula, if the integer p becomes more than 4, thereactivity of the ethylenically unsaturated group of the phosphoricester lowers and the crosslinking property of the composition becomesworse, which is not preferable. Said alkylene phosphate esters can beobtained by neutralizing the above-mentioned alkylene phosphoric esters.The bases or chlorides as used for such neutralization may be those asdisclosed in the foregoing explanation of the sulfonic esters. Thisneutralization may be carried out also according to the ordinarily knownmethod.

The phosphoric diesters which are used in the present invention arealkylene phosphoric diesters or alkylene phosphate diesters of acrylicacid or methacrylic acid. As for the alkylene phosphoric diesters ofacrylic acid or methacrylic acid, for example,

phosphoric bis(ethyleneacrylate), phosphoric bis(ethylenemethacrylate),phosphoric bis(trimethyleneacrylate), phosphoricbis(isopropylenemethacrylate), phosphoric bis(trimethylenemethacrylate),phosphoric bis(tetramethyleneacrylate) and phosphoricbis(tetramethylenemethacrylate) may be used. In the foregoing generalformula, if the integer q becomes more than 4, the reactivity of theethylenically unsaturated group of the phosphoric diester lowers and thecross-linking property thereof becomes worse, which is not preferablefor the object of the invention. Further, said alkylene phosphatediesters can be obtained by neutralizing the above-mentioned alkylenephosphoric diesters. The bases or chlorides as used for suchneutralization may be those as disclosed in the foregoing explanationwith regard to the sulfonic esters.

The epoxy compounds which are used in the present invention, aremiscible with the above sulfonic esters, phosphoric esters andphosphoric diesters, and are the compounds containing epoxy groups inthe molecules. Such epoxy compounds having epoxy equivalent of 100 g. to2000 g./mole of epoxy group are, for example, a polymer (having numberaverage molecular weight of about 2000 to about 5000) of the ester ofglycidol and acrylic acid or methacrylic acid; a copolymer (havingnumber average molecular weight of about 2000 to about 5000 andcontaining above ester of more than 20% by weight) of the above esterwith ethyl acrylate, methyl methacrylate, styrene, vinyl chloride orvinyl acetate; a reaction product of epichlorohydrin and bisphenol A; areaction product (having number average molecular weight of about 10,000to about 100,000) of cellulose derivative and epichlorohydrin; or areaction product (having number average molecular weight of about 10,000to about 100,000) of polyvinyl alcohol and epichlorohydrin.

The composition of the present invention comprises from 25 to 85% byweight of one or more members selected from the group consisting of theabove-mentioned sulfonic esters, phosphoric esters and phosphoricdiesters, and from 75 to 15% by weight of one or more members of theabove-mentioned epoxy compounds, as the principal components. It is notdesirable to decrease the content of the epoxy compounds less than 15%by weight, because the film forming property becomes worse, and therebythe excellent mechanical properties, solvent resistance, surfacehardening and adhesiveness of the obtained film cannot be expected.Further, it is also not desirable to increase the content of the epoxycompounds more than 75% by weight, because the electroconductivity ofthe obtained film is decreased. As defined in the above, when the epoxycompounds are solid state at the room temperature and more than 50 to60% by weight of the epoxy compounds are used for the mixture of thecomposition, the mixture is liable to become hard to deal with, as theviscosity thereof is increased. Therefore, it is preferable to dilutethe mixture of the composition with the solvents such as hydrocarbons,alcohols, ketones or esters. Further, in case that the composition whichis diluted with the solvents is cured by ionizing radiation or actinicrays, it is desirable to apply the irradiation after the evaporation ofsuch solvent in the coated film.

The composition of the present invention is cured by two kinds ofsimultaneous cross linking reactions by heating or irradiation ofionizing radiation or actinic rays, that is, one is the cross linkingreaction between the ethylenically unsaturated bonds contained in one ormore compounds selected from the group consisting of sulfonic esters,phosphoric esters and phosphoric diesters, and the other is the ionicreaction between the metallic ion M in the above compounds, as specifiedin the foregoing general formulae, and the epoxy group in the epoxycompound.

The curing by heating of the composition of the present invention may becarried out by applying the composition with the heat at a temperaturefrom the room temperature to 150 C., preferably in the range from 50 toC., for 1 to 60 minutes, in the presence of the ordinarily usedpolymerization initiators such as benzoyl peroxide, hydrogen peroxide,methy ethyl ketone peroxide, azobisisobutyronitrile, lauroyl peroxide,azobisdimethyl valeronitrile, diisopropyl peroxycarbonate, t-butylperoxypivalate, acetylcyclohexyl sulfonyl peroxide, 1,1-az0-1-chloro-l-cyanobis (l-phenyl ethane) or di-t-butyl peroxide, or withoutusing such polymerization initiators. In the above-mentioned heatcuring, it is not desirable to heat at a temperature above C. becausethe foaming of the film is caused to occur.

The curing of the composition by the application of actinic rays may becarried out by irradiating the actinic rays with the wave length ofabout 2500 to about 6000 angstroms in the presence of one or more of thecompounds selected from the above-mentioned polymerization initiators,and other ordinary photosensitizers such as aazobis-l-cyclohexanecarbonitrile, diphenyl disulfide, tetramethylthiuram monosulfide,tetramethylthiuram disulfide, benzoin, benzoin ethyl ether,anthraquinone, biacetyl, benzophenone, acetophenone,9-bromoacetophcnone, uranyl nitrate, silver perchlorate and ferricchloride.

Further, the composition of the present invention may be cured by theapplication of ionizing radiations such as electron beam and otherradiant rays, in this case, no particular polymerization initiator isnecessary, however, the above-mentioned peroxides or azo-compounds maybe contained as the polymerization initiators without any substantialtrouble.

When the above-mentioned photosensitizers and polymerization initiatorsare used for the composition of the present invention, the amountthereof may be 10% or less by weight, and preferably 7% or less byweight.

In addition to the above components, the composition of the presentinvention may be added with surface active agents and metallic salts, inorder to improve the electroconductivity of the film obtained. That is,for example, metallic salts, sulfates and phosphates of carboxylic acidsas anion surface active agents; amine salts and pyridinium salts ascation surface active agents; and salts of carboxylic acids, sulfuricesters and of phosphoric esters as ampholytic surface active agents maybe used. Further, as the metallic salts, zinc chloride, aluminumchloride, antimony chloride, indium chloride, calcium chloride, goldchloride, cobaltous chloride, stannous chloride, stannic chloride,ferrous chloride, ferric chloride, cuprous chloride, cupric chloride,zinc sulfate, aluminum sulfate, copper sulfate, sodium sulfate, ironphosphate, copper phosphate, zinc phosphate, silver phosphate and silverper chlorate, may be used. The amount of these surface active agentsand/or metallic salts being added into the composition of the inventionmay be 20 parts by weight or less against 100 parts by weight of saidcomposition. And if more than 20 parts by weight of the surface activeagents and/or metallic salts is used for the composition, the mechanicalproperties and solvent resistance of the resin obtained become worsewhich is not desirable.

As disclosed in the above, the composition of the present invention iscured by the cross linking reaction, and the electric resistance of thecured resin of the invention is only to 10 ohms in the surface specificresistance and the volume specific resistance at a relative humidity of70%, which value is surprisingly only one-hundredth to one-tenthousandth @5 to as compared with those of the conventionalelectroconductive resins. Further, the conventional electrotroconductiveresins have the defect that it is subject to the influence of humidityand when the humidity becomes low, the electroconductivity of suchresins is decreased. While the resin formed by the composition of thepresent invention is not influenced by the humidity and has theexcellent electroconductivity as disclosed in the above, this excellentproperty is considered to be the result of the very high density of theintermolecular cross linkage.

The composition of the present invention is cured by cross linkingreaction through the application of heat rays, actinic rays or ionizingradiation. Accordingly, as compared with the conventional evaporationdrying type ones, the solvent resistance, mechanical properties, etc. ofthe product of the composition of the invention are remarkablyexcellent. Further, the synthesis of each component of the compositionof the present invention is easy and economical, and in addition to thatthere is no fear of gelation of the component during the synthesis.Still further, free hydroxyl groups are contained in the molecule of thecured resin, as the epoxy compounds participate the cross linkingreaction of the composition, therefore the adhesiveness to the substratecan be very much improved, and the cross linking reaction in the portionbeing contacted with oxygen in the air is not inhibited, as the result,an excellent composition with good friction resistance and withoutsurface tackiness can be obtained. Accordingly, the composition of thepresent invention is quite different from the conventional ones in thestructures, and the efiects obtained from the composition of theinvention are beyond the ordinary conception. The composition of thepresent invention can be used for various purposes, especially forfacsimiles, microfilms, mag- 6 netic recording tapes, video recordingtapes and electroconductive papers.

The following Examples show various aspects of the invention in greaterdetail. It should be understood, however, that these are onlyillustrative. Other combinations and variations from the embodimentsshown will no doubt occur to those skilled in the art. These areconsidered to be part of the invention.

EXAMPLES 1 TO 38, AND COMPARATIVE EXAMPLES 1 TO 4 Each component asindicated in the following Tables was weighed and mixed together withother components to form each composition. The method for curing foreach composition was as follows:

A Petri dish (10 cm. in diameter and 1.5 cm. in depth) was fed withmercury to form a mercury layer. One of the compositions of the Exampleswas poured on said mercury layer so as to form a cured film of 100microns in thickness, then the cover was fixed for one hour in order tore move the foam contained. Thereafter, the cover was taken off, and ifa solvent was used for the composition, the dish was allowed to standstill at the room temperature for removing such solvent. Thus obtainedsample was cured under the conditions as indicated in the Table withusing light rays, ionizing radiation or heating to form a curedelectroconductive film. Then the electroconductivity and the tensilestrength of the obtained film were measured.

Meanwhile, each composition of the Examples was applied to Lumilar-T100(trade name of polyethylene terephthalate film made by Toray IndustriesInc., Japan) so as to form a cured film of 100 microns in thickness. Andit was cured under the conditions as indicated in the Table with usinglight rays, ionizing radiation or heating. Then the obtained cured filmwas used for testing the water resistance, solvent resistance and pencilhardness.

It will be understood in accordance with the results as shown in thefollowing Tables that the cured films obtained from the compositions ofthe present invention are excellent in the electroconductivity, waterresistance, solvent resistance, mechanical property (tensile strength)and surface hardness (pencil hardness), as compared with those of theordinarily known ones. Further, the surprising fact is that thetransparency, an adhesiveness, shock resistance and film formingproperty of the film obtained from the composition of the presentinvention are also remarkable.

TABLE 15 Composition ('1) Phos- P 1 Sultome Phosphoric phoric Epoxyiiiiti iz rii :1 on Other Ex. ester ester dlester compound Solventphotosensitizer additive 1 SEM (*7) [25]-. Epikote 1004 (39) Methylethyl .5 ketone [20]. 2 SEA 8) [5.0] Gig-02080 ('40) Acetone [20] s SBA(*9 [8.5]-.. on sbso 41) [1.5] AIBN *51 0.7 4 SEM-Cl (*10 [2. PVA-Ep(*42) 17.51-- Acetone [2o] BPO 52) [o .5 IIII 5 SEM [2.5]. Etlgl-Ep (43)Acetone [20]; DBPO (53) [0.1]... Neogen-R ('60) 6 Ph2os5mer-M (18) (2.5](1113 8020 (44) [7.5] Benzene [1[C]] LPO (54) [0.3]

acetone 10 7 Phosmer-MA (19) GMA-H (45) [5.0]. Ethyl acetate [10] ABVN(55) [0.6]. Teepol B81 5.0 acetone [10]. ("61) [2.5]. Phosmer-Cl ('20)[8.5] GM-8020 [1.5]

See notes at end of Table 6b.

TABLE 11) Curing condition Test results of electroconductive filmElectroconduetivity (*2) Measuring condition Surface Volume Tempera-Temperaspecific specific Water Solvent Tensile Pencil ture Time Moistureture resistance resistance resistreslststrength hard C.) (min.)(percent) 0.) (011m) (ohm-em.) ance("3) once (*4) (kg.) (5) ness(*6)Example:

1 100 10 40 2O 8.5)(10 7.1 10 50 10 1.8 HB

100 10 40 20 1. X10 0.8 50 10 1.6 B 100 3 40 20 2.1)(10 1.9 10 25 5 1.4313 100 3 40 20 .'5.4 10 2.6)(10 10 5 1.0 38 100 3 40 20 4.6 10 3.9 10-"20 10 2.0 313 80 5 40 20 9.8)(10 3.1 10 50 10 2.5 B 50 40 7.6)(10 4.4X1050 10 3.0 B 140 40 20 1. 2x10 3.5 10 10 1.7 2B

See notes at end of Table 6b.

TABLE 2a Composition Polymerization initiator or w photo- Ex. Sulfonicester Phosphoric ester Phosphoric diester Epoxypompound Solventsensitizer Other additive Q Phosmer-MD (*29) [45].- GB5-51090 (46)Acetone [20]"--. BIl2 (56) m PhosiIIner-CID Cali-i311) (47) CS P. (57)Niglrel powder 11 SEM [2.5] Phosmer-M [2.5] (lelfie ltp (*48) Acetone[20]... AIBN [0.6]. Coppeg'powder 12 SEM [2.0] Phosmer-CID [5.0]Epikote1004(3.0] Copper powder 13 Phosmer-M [4.0] Phosmer-MD CelAe-Ep[1.5] BPO [0.1] 14 SEM [1.0]- Pl1osmer-Cl[l.0] Phosmer-MD [2.0] CAP-Ep[6.0] Methyll-eettglzglmw BPO [0.1]-.. 15.--" SEN-Ne. (*11) [2.5] OAP-Ep[7.5] do BPO [0.1].-- Antimony chloride 16 Phosmer-M-Li (*21)GE-8020[5.0] -.do BPO 0.1 indium' ill r See note at end of Table. 6b.

TABLE 2b Curing condition Test results of electroeonduetivc filmElectroconductivity (*2) Measuring condition Surface Volume Tempera-Temperaspecific specific Water Solvent Tensile Pencil ture Tune Moistureture resistance resistance resistresiststrength hard- 0.) (min.)(percent) 0.) (ohm) (ohm cm.) ance(*3) 21110004) (kg.) (*5) ness("6)Example:

120 2 40 20 x10 6.7)(10 50 10 2.2 B 2 40 20 4. 9X10 2. 1X10 50 10 1. 1HB 100 2 40 20 2. 0X10 2. 0X10 50 10 0. 9 B 100 2 40 20 5. 6X10 2. 1X1050 10 1. (J B 100 2 40 20 4. 2X10 3. 7X10 50 10 2. 5 B 100 2 40 20 45X10 2. 9X10 5O 10 2. 1 B 100 2 40 20 1 1X10 1.9Xl0 20 5 1.5 4B 100 2 4020 9 2X10 8. 1X10 20 5 1. 5 413 See notes at end of Table 0b.

TABLE 3:).

Composition Pol merization Suli'onic Phosphoric Phosphoric initl ator orOther Ex. ester ester diester Epoxy compound Solvent photosensitizeradditive 17 SBA-011012) [4.5] GE1090(*49) [5-5] Met y ethyl BPO [0.1]Ferric chloride ketone [20]. [2.0]. 18 ri ng [Dan GE-3070 (*50) [7.5]BPO [0 ll Zinc oxide 2. .5 19 Phosmer-Cl-Al CelAe-Ep [3.0] LPO [0.7]Titlm m phosphate 20 SEA-NH; (*13 4.0 Phosmer-M-dime- CAP-Ep 4.0 KW-8 53[0.e]

tzhgllamine (*23) 21 Phosmer-Cl-n- Phosmer-CID- Epikote 1007 *39 5.0Acetone 20 KW-s [0,6]

butylamine triethanolamine (24) [2.5]. (*32) [2.5]. 22 SEM-pyndme (14)Phosmer-MD-p- Epikote 1000 (39) [7.5] ..do AIBN [0.7]

[1.0]. phenylene diamine (*35) [1.5].

See notes at end of Table 6b.

TABLE 3b Curing condition Test results of electroconductive filmMeasuring condition Electroconduotivity Surface Volume Temper- Mois-Temperspecific specific Water Solvent Tensile Pencil ature Time tureature resistance resistance resistresiststrengt hard- 0.) (min.)(percent) 0.) (ohm) (ohm-cm.) ance ance (kg.) ness 100 2 40 20 1.2)(103.6)(10 20 1.5 413 100 2 40 20 2.4)(10 7.1)( 20 4 2.0 BR 150 1 40 20 2.2x10 1. 5X10 1. 5 43 Light irradiation 50 10 40 3.4X10 2.6)(10 10 3 1.56B 10 20 6.7)(10 8.2)(10 12 3 1.9 SE

Temperature C.)

Time (min.)

See notes at end of table 6b.

TABLE 4a Composition Phos- Polymerization Phosphoric phoric Epoxyinitiator or oth Ex. Sulfonic ester ester dlester compound Solventphotosensitizer additi 23 SEM-ethylenediamine(*15) [5.0] Epikote 1004[50].. Acetone [20]... AIBN [0.7] 24, SEM 15.0 GE-8020 [5.0 do. 25SEM150 CCBPE (*59) [0.7]

AIBN [0.7 AIBN [0.7 AIBN [0.7

See notes at end of Table 6b.

TAB LE 4b Curing condition Test results of electroconductive filmMeasuring condition Electroconductivity Surface Volume Temper- Mois-Temperspecific specific Water Solvent Tensile Pencil ature Time tureture resistance resistance resistresiststrength hard- 0.) (min.)(percent) 0 (ohm (ohm-cm.) ance ance (kg.) ness Example: 23 100 1 40 206. 9X10 4 9. 9X10 5 50 10 2. 0 6B Electron beam 40 2O 2. 2X10 4 2.0Xl020 4 1. 5 2B irradiation (*63) 20 30 40 20 2.1X1O 5 2. 1X10 5 5 1 1. 06B 100 6 20 2.3)(10 4 1.5X10 4 50 10 2.0 B 6 40. 20 7.4 10 6.5)(10 50 102.0 B 100 6 15 20 9.1X10 4 9. 6X10 4 50 10 2. 0 B 100 5 40 20 1. 1X104 1. 5X10 4 20 10 1. 5 4B TABLE 5a Composition I Polymerizationinitiator or photo- Other Example Sulionic ester Phosphoric esterPhOSDhOIlG diester Epoxy compound Solvent sensitizer additive 30 SEA-Al[20].--- Phosmer-M-pyridine salt GMA [6.0] Methyl ethyl (*25) [2.0].ketone [20]. 31 SEM-diethyl- Phosmer-MDA ('34) [20]...- GMA [5.0] dogmo'lne (17) Phosmer-MA-p-phenylene- Phosmer-MDA-Li (*35 PVA-Ep Nickeldiamine salt (*26) [1.0]. [4.5]. powder 3.0 33 Phosmer-MD-ethylene-EtCel-Ep [25].... copp er diamine (36) [7.5]. powder 3.0 34 SEM [1.0]Phosmer-Ol-ethylene- Phosmer-ClD-Al (37) [4.51" CelAc-Ep [3.5]

diamine [1.0]. 35 Phosmer-ClD-morpholine CelAc-Ep [4.5]...- Tetrahydro-(38) [5.5]. iuran [20]. 36 Phosmer-Cl-Mg (*28) [7.5] CelAc-Ep [2.5]

See notes at end-of Table 6b.

TABLE 5b Test results of electroconduetive film ElectroconductivityCuring condition Measuring condition Surface Volume Temper- Mois-Tcmpcrspecific specific Water Solvent Tensile Pencil ature Time tureeture resistance resistance resistresiststrength hard C.) (min.)(percent) 0.) (ohm) (ohm-cm.) ance ance (kg) ness 100 5 40 20 5. 6X10 6.5X10 25 10 2.0 33 100 5 40 20 4.1)(10 2.5)(10 50 10 2.1 4B 100 5 40 2O4. 5X1() 1. X10 50 10 1. 4 B 100 2 40 20 1.4)(10 4.5X10 50 10 1.4 B 1002 40 2O 4. 1X10 9. 7X10 50 10 2. 2B 100 2 40 20 6. 9X10 1. 0X10 5O 2. 52B 100 2 40 20 7. 5X10 2. 0X10 5O 10 2. 1 B

TABLE 6a Composition Comparative example:

1-.. EOE-34 (made by The Dow Chemical Company).

Do. Do. 4 A sheet which is mixed with electroconductive carbon (filmthickness 100microns).

TABLE 6b Test results of electroconductive film ElectroeonductivityCuring condition Measuring condition Surface Volume Temper- Mois-Temperspecific specific Water Solvent Tensile Pencil Comparative atureTime ture ature resistance resistance resistresiststrength hardexampleC.) (hour) (percent) 0.) (ohm) (ohm-cm.) ance ance (kg.) ness 1.-. Room3 70 25 21x10 4.0)(10 0.5 0.5 0.1 Below temp. 6B. 2.-. do 3 50 25 2.2X10 4.0)(10 0.5 0.5 0.1 Do. do 3 25 1.0)(10 9. 8X10" 0. 5 0. 5 0. 1 D0.do 3 50 4.5X10 2. 6X10 50 6 0.4 Do.

b 1) 'ghe nuntierals in the brackets in the columns of components forthe composition indicates respective amounts as used,

y parts y woig t.

('2) The electrcconductivity was measured as follows: As the measuringapparatus, Electrode TR-42 for measuring ultra high resistances (made byTakeda Riken, Japan) and an ainmeter (made by Yokokawa Electric Works,Limited, Japan) were used. The measurements were carried out inaccordance with JISK-0723 and "Plastic Testing Handbook (published byNikkan Kogyo Shiinbuirsha, Japan).

(*3) Each test piece was immersed into water at a temperature of 20 C.and the period to become cloudy of the clectroconductive film wasmeasured. Each numeral as indicated is represented by days.

(4) Each test piece was immersed into chlorobenzene at a temperature of20 C. and the period to become cloudy of the electroconductive film wasmeasured. Each numeral as indicated is also represented by days.

(5) Each test piece with the size of 10-20 mm. was put to the test withusing Tcnsilon" Universal Tensile Testing Machine, Model UTM-II (made byToyo Sokki Kabushiki Kaisha, Japan) at a temperature of 20 C. and atensile rate of 20 mm./min.

(*6) Pencil hardness was measured in accordance with J IS-K5652.5.15 ata temperature of 20 C.

(7) SEM represents 2-sulfoethylene methacrylate.

(8) SEA represents 2-sulfoethylene acrylate.

(*9) SBA represents 2-suliotetramethylene acrylate.

(* 10) SEM-C1 represents 2-sulio-2-chloroethylene methacrylate.

(11) SEM-NA represents sulfonic ester which is obtained from 1 mole ofSEM and 1 mole of NaOH.

(*12) SBA-Cu represents sulfonie ester which is obtained from 2 moles ofSBA and 1 mole of Cu(OH)=.

(13) SEA-NH; represents sulfonic ester which is obtained from 1 mole ofSEA and 1 mole of ammonia.

(14) SEM-pyridine represents sulfonic ester which is obtained from 1mole of SEM and 1 mole of pyridine.

('15) SEM-ethylenediamine represents sulionic ester which is obtainedfrom 2 moles 01 SEM and 1 mole of ethylenediamlne (*16) SEA-Alrepresents sulfonic ester which is obtained from 3 moles of SEA and 1mole of Al(OH);i.

(17) SEM-dicthylamine represents sulionic ester which is obtained from 1mole of SEM and 1 mole of diethylamine.

(18) Phosmer-M represents phosphoric ethylene methaerylate.

('19) Phosmer-MA represents phosphoric ethylene acrylate.

(20) Phosmer-Cl represents Z-phosphoric-2-chloroethylene methacrylate.

(21) Phosmer-M-Li represents phosphoric ester which is obtained from 1mole of phosmer-M and 2 moles of LiOH.

("22) Phosmer-Cl-Al represents phosphoric ester which is obtained from 3moles of Phosmer-Cl and 2 moles of Al(0 11);. d1 ("5)1Phosmer-M-dimethylamine represents phosphoric ester which is obtainedfrom 1 mole of Phosmer-M and 2 moles of met y amine. b t(124)Phosmer-Cl-n-butylamine represents phosphoric ester which is obtainedfrom 1 mole of Phosmer-Cl and 2 moles of nu y armne.

(25) Phosmer-M-pyridine salt represents phosphoric ester which isobtained from 1 mole of Phosmer-M and 2 moles of pyridine.

(26) Phosiner-MA-p-phenylenediamine salt represents phosphoric esterwhich is obtained from 1 mole of Phosrner-MA and 1 mole pfp-phenylenediamine.

th (1'27)d1Phasmer-Cl-ethylenediamine represents phosphoric ester whichis obtained irom 1 mole of Phosmer-Cl and 1 mole of e y ene am rie.

(28) Phosmer-Cl-Mg represents phosphoric ester which is obtained from 1mole of Phosmer-Cl and 1 mole of Mg(OH)a.

(29) Phosmer-MD represents phosphoric bis (ethylene niethecrylatc).

(30) Phosmcr-CID represents the compound as defined by the followingformula:

('31) Phcsmer-MD-Zn represents phosphoric diester which is obtained from2 moles of Phosmer-MD and 1 mole of Zn(0H)2. It fig)Phosincr-CID-triethanolamine represents phosphoric diester which isobtained from 1 mole oi Phosmer-ClD and 1 mole o no ano amine.

("33) Phosiner-MD-p-phenyienediamine represents phosphoric diester whichis obtained iroin 2 moles of Phosmer-MD and 1 mole ofp-phenylenediamine.

(34) Phosmer-MDA represents the compound as defined by the followingformula:

FOOTNOTE SContinued (*35) Phosmer-MDA-Li represents phosphoric diesterwhich is obtained from 1 mole of Phosmer-MDA and 1 mole of LiOH. (*36)Phosmer MD-ethylenediamine represents phosphoric diester which isobtained irom2moles of Phosmer-MD and 1 mole of ethylenediamine.

(*37) PhnsmerClD-Al represents phosphoric diestcr which is obtained from3 moles of Phosmer-CID and 1 mole of AI(OH)3. (*38)Phosmer-ClD-morpholine represents phosphoric diester which is obtainedfrom 1 mole of Phosmer-ClD and 1 mole of morpholine.

(*39) Epikote 1004, Epikote 1007, and Epikote 1009 are the trade namesof the epoxy resins which are made by Shell Chemical Co., Ltd. Theseepoxy resins are polyglycidyl ethers of bisphenol A.

(*40) GE-2080 represents a copolymer of glycidyl methacrylate/cthylmethacrylate=20/80 (weight ratio), and the copolymer has a numberaverage molecular weight, of about 15,000 and epoxy equivalent of 602g./mole of epoxy group.

(*41) GEE-5050 represents a copolymer of glycidyl methacrylate/ethylmcthacrylate=50l50 (weight ratio), and the copolymer has a numberaverage molecular weighi'of about 5,800 and epoxy equ valent of 250gJmolc of epoxy group.

(*42) PVA-Eprc presentstlie reaction product of 100 parts by weight ofpolyvinyl alcohol and 25 parts by weight of epichlorohydrn; The producthas a number average molecular weight of about 100,000 and epoxyequivalent of 452 gJmole of epoxy group.

(*43) EtCel-EP represents the reaction product 01100 parts by weight ofethyl cellulose and 22 parts by weight of epichlorohydrin. The producthas a number average molecular weight of about 25,000 and epoxyequivalent of 465 g ./mole of epoxy group.

(*44) GE-8020 represents a copolymer oi glycidyl methacryl ate/cthylmethacrylate=80l20 (weight ratio) and the copolymer has a number averagemolecularweightfaboi1t3,500 and epoxy equivalent of 175 g./mole of epoxygroup.

(*45) GMA-H represents a pol 2,000 and epoxy equivalent of 145 g. moleof epoxy group.

er of glycidyl methacrylate, and the polymer has a number averagemolecular weight of about 46) GB-1090 represents a copolymer of glycidylmethacrylate/butyl methacrylate=10l90 (weight ratio), and the copolymerhas a number rage molecular weight of about 10,000 and epoxy equivalentof1,420 g./mole of epoxy group.

:4 AP-Er) represents the reaction product of 100 parts by weight ofcellulose acetate phth alate and parts by weight of epichlorohydrin. Theproduct has a number average molecular weight of about 30,000 and epoxyequivalent of 1,850 g./mole of epoxy roup.

(*48) Cel Ac-Ep represents the reaction product of 100 parts by weightof cellulose acetate and 35 parts by weight of epi hl h duct has anumber average molecular weight of about 15,000 and epoxy equivalent01'380 g. [mole of epoxy group. 8 i 1090 represents a copolyme'r'ofglycidyl methacrylate/ethyl methacr late= g (weight ratio) and the 0 Op01 may has a number average molecular weight of about 40,000 and epoxyequivalent of 1 ,170 g. mole of epoxy group,

'50) GE-3070 represents a copolymer o g yc y methacrylate/ethvl metaei-y ate=3c/70 (Welght ratio), and the copolymer has a number averagemolecular weight of about 10,000 and epoxy equivalent of410 ./m 1 ofepoxy group (51) AIBN represents azobi isobntyronitr1le ("52) BPOrepresents benzoyl peroxide.

('53) DBPO represents di-t-butyl peroxide.

(54) LPO represents lauroyl peroxide;

(* *55) AB VN represents azobisdimethyl valeronitrile. (56) BPPrepresents t-butyl peroxyprivalate.

(57) ACSP represents acetylcycloh xyl-sulfonyl peroxide. ('58) KW-8represents benzoin ethyl ether.

('59) ACCBPE represents 1,1-azo-lfiohloro-Y-cyanobis(1-phenylethane).

en-R is a trade name of anion surface active agent which is made byDai-ichi Kogyo Seiyaku Co. Ltd. Japan. 0% i e iggol B81 is a trade nameoffanion surface active agent .vhich 18 made by Dai-ichi Kogyo Seiyaku0b., Ltd., Japan.

("62) The conditions of the light irradiation were as follows Lightsource: High pressure mercury lamp H-400P (400 watt) made by TokyoShibaura Electric 00., Ltd., Japan. Distance between the light sourceand the surface to be irradiated: 50 cm.

Curing conditions: As indicatedin the table. (63) The conditions of theelectron beam irradiation were as follows- Electron beam: Density ofabout 50 a./cm.2 which is accelerated by the acceleration voltage of 250kv.

Dose of beam: 1 Mrad.

What is claimed is:

1. A composition for preparing .electroconductive resin which comprises:

(a) one or more members selected from the group consisting of:

(I) compounds represented by the following general formula:

in which R is a hydrogen atom or a methyl group; each of R and R is ahydrogen or halogen atom; n is an integer from 1 to 5; x is an integerfrom 1 to 3; and M is a hydrogen atom, Na, Li, K, Ag, Cu, Mg, Ca, Zn,Ba, Al, am monium or amine,

(II) compounds represented by the following general formula:

l. t. J. L

in which R is a hydrogen atom or a methyl group; each of R and R is ahydrogen or halo- 75 E10 l in gen atom; q is an integer from 1 to 4; xis an integer from 1 to 3; and M is a hydrogen atom, Na, Li, K, Ag, Cu,Mg, Ca, Zn, Ba, Al, ammonium or amine, and

(B) compounds which contain vicinal epoxy groups in the molecules.

2. An clectroconductivc composition as claimed in claim 1, in which saidcomposition is further added with solvents, polymerization initiatorsand/or photoscnsitizers.

3. An electroconductivc composition as claimed in claim 1, in which theamount of the compounds as de fined in paragraph (A) of claim 1 is inthe range of 25 to parts by weight and the amount of the compounds asdefined in paragraph (B) of claim 1 is in the range of 75 to 15 parts byweight.

4; An electroconductive composition as claimed in claim 1, in which theglass transition temperatures of the compounds as defined in paragraph(B) of claim 1 are higher than 310 K.

5. An electroconductive film which is prepared by applying light rays,heat, actinic rays or ionizing radiation to the resin formed of thecomposition as claimed in claim 1.

6. The elcctroconductive composition of claim 1, in which said compoundscontaining epoxy groups in the molecules are at least one selected fromthe group consisting of glycidyl acrylate homopolyrnor, glycidylmethacrylatc homopolymer and copolymers of glycidyl acrylate and/orglycidyl mcthacrylate with at least one of vinyl monomers consisting ofethyl acrylate, methyl methacrylate, styrene, vinyl chloride and vinylacetate.

7. The electroconductive composition of claim 1, wherein said epoxycompounds of paragraph (B) are polymers. comprising esters of glycidoland acrylic acid or methacrylic acid, said epoxy compounds having epoxyeqnivalent of g. to 2000 g./mol.

8. The electroconductive composition of claim 1 wherein said epoxycompounds of paragraph (B) are copolymers of esters of glycidol andacrylic acid or methacrylic acid and a vinyl monomer, said esterscomprising more than 20% by weight of said copolymer.

9. The electroconductive composition of claim 6 wherein the epoxycompounds of paragraph (B) comprise from 15% to 75% of the weight ofsaid electroconductive composition.

10. The electroconductive composition of claim 6 prepared as a film bycross-linking using heat.

11. The electroconductive composition of claim 1 wherein said compoundswhich contain vicinal epoxy groups in the molecules are a reactionproduct of epichlorohydrin and bisphenol A.

12. The electroconductive composition of claim 1 wherein said compoundswhich contain vicinal epoxy groups in the molecules are a reactionproduct of ethyl cellulose, cellulose acetate, or cellulose acetatephthalate with epichlorohydrin.

13. The electroconductive composition of claim 1 wherein said compoundswhich contain vicinal epoxy groups in the molecules are a reactionproduct between polyvinyl alcohol and epichlorohydrin.

References Cited UNITED STATES PATENTS OTHER REFERENCES Lee & Neville:Hand book of Epoxy Resins, pp. 1-1 and 1-2, McGraw-Hill, 1967.

WILLIAM H. SHORT, Primary Examiner 15 E. A. NEILSEN, Assistant ExaminerU.S. Cl. X.R.

117-161 ZB; 204-15922; 260-23 EP, 47 EP, 79.3 M, 86.1 N, 86.1 R, 89.5 R,91.3 VA

UNITED STATES PATENT OFFICE CERTIFICATE 0F CORRECTION P t t N 3,847,846Dated November 12, 1974 Inventor s) Kiyohiko ASADA It is certified thaterror appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

Column 2, line 3, "Al ammonium" should be --Al, ammonium--.

Column 2 line 19 "M" in the formula should be -M Column 4, lines 29 and30 "l,l-azo-l-chloro-l-cyanobis" should be --l,l'azo-l-chlorol-cyanobis-.

TABLE la, Ex. 6, "Phosmer-M (*18) (2 .5] [2.5] should be -Phosmer-M(*18) [2.5]

TABLE la, after Ex. 7 should be 8 TABLE 2a, Ex. 12 "Epikote 1004 (3.0]should be -Epikote 1004 [3.0].

TABLE 4a, Ex. 24, "SEM 15.0] should be -SEM [5.0]

TABLE 4a, Ex. 25, "SEM 15.0] should be -SEM [5.0]-.

TABLE 4a Ex. 29, "SEM-Cl 17.5" should be -SEMC1 [7.5]--.

Column 11, footnote (*26) line 2 "pf" should be of--.

Column 13, footnote (*43) "EtCel-EP" should be -EtCelEp- Column 13,footnote (*56) "peroxyprivalate" should be -peroxypivalate--.

Column 13, footnote (*63) line 2 "50 ca./cm. should be --50 -A/cm Column13, line 38, (a) should be (A).

Signed and sealed this 1st day of April 15 75.

Atte

M q C. lL=-.RSIEALL Zl-tNI-Y no C, LIASCA Commissioner of Patentsi-'-.ttest1ng 0; floor and Trademarks

1. A COMPOSITION FOR PREPARING ELECTROCONDUCTIVE RESIN WHICH COMPRISES:(A) ONE OR MORE MEMBERS SELECTED FROM THE GROUP CONSISTING OF: (I)COMPOUNDS REPRESENTED BY THE FOLLOWING GENERAL FORMULA: